Cloth containing antivesicant



United States Patent Ofi ice No Drawing. I Application March 29 1933 Serial No. 664,199 9 Claims. (Cl. 1l7-1Z1) (Granted under Title 35, US. Code (1952), see. 266) The invention described herein may be manufactured and used by or for the Government for governmental purposes, without the payment to me of any royalty thereon.

This invention relates in general to the destruction of mustard gas, (bis(beta-chlorethyl)sulfide) by the chloramines of aromatic carboxy acids and the chloramines of sulphonic acids and more particularly has reference to a method of treating materials to render them resistant against vesicant gases, vapors and liquids and to the treating agents and the resulting product.

This application is a continuation-in-part of my copending application Serial Number 602,114, filed March 30, 1932, now abandoned, for Impregnite B.

It has long been sought to devise a clothing or covering to protect persons against vesicant gases, particularly mustard gas. Vesicants of this character, as is well known, penetrate ordinary clothing and produce serious irritations of the skin tissue, sometimes causing death.

In order to render clothing and the like resistant against the penetration of such vesicants as mustard gas, the same has been more or less effectively impregnated with chlorinating agents in various forms. this character such as have been used on cloth in the past, however, possess the disadvantage that in all cases the protecting agent quickly decomposes on exposure to sunlight and air, so as to completely negative its efiectiveness after a short period of time. It will be appreciated, therefore, that the various agents previously employed while of a sufficient degree of activity to convert vesicant gases such as mustard gas into'a non-injurious form, have been very unstable, so that their effectiveness as impregnants has been negatived for practical purposes.

The chloramines in general possess the desirable destructive action upon mustard gas and other vesicants. When impregnated in cloth they react with suflicient rapidity to prevent penetration of the cloth by mustard gas. The chlorine attached to the nitrogen atom reacts with mustard gas to render the same non-vesicant.

The principal chloramines, namely those of sulphonic acids such as chloramine-T and dichloramine-T, and of carboxy acids are exceedingly effective compounds for the destruction of .mustard gas. However, certain of the chloramines when impregnated into cloth are not as stable as is desirable.

An object of this invention is to render clothing resistant to the penetration of such gases as mustard, without rendering the cloth impermeable to the passage of air and transfer of body moisture.

Another object of this invention is to provide compounds which react with mustard gas and similar vesicant compounds to render them harmless.

Another object of this invention is to provide a more efiective salve forthe treatment of mustard gas burns.

A further object of this invention is to-provide clothing impregnated with a stabilized chloramine of a carboxy acid.

With these and other objects in view, the invention consists in the ingredients and steps to be hereinafter set forth and claimed, with the understanding that the several The impregnants of means of sodium hypochlorite;

necessary substances and compounds employed in carry-- steps involved in the proce-- without departing from the spirit of the invention or the scope of the appended ing out the invention, and the dure may be widely varied claims.

The chloramines of sulphonic acids such as chloramine- T and dichloramine-T and the chloramines of carboxy' acids are excellent destructive agents for the conversion of such vesicants as mustard gas into non-vesicant compounds.

Dichloramine-T (toluene-p-sulphondichloramide) may be prepared by adding the corresponding sulphonamide to an excess of a saturated solution of bleaching powder,. in which it readily dissolves, and then slowly pouring; acetic acid into the cooled solution. The sulphondichlor-- amide at once separates as an oily liquid which solidifies quickly to white crystalline solids. These may be filtered? off and are practically pure. As however, this solid is not easily and conveniently dried, it is best to addto the: acid liquid sufiicient chloroform to dissolve the solid completely. It is advisable to shake the chloroform solution with a further smallquantity of fresh acidified bleaching'powder solution to insure the absence of any trace of unchanged sulphonamide. The chloroform solution is then separated, dried over fused calcium chloride, and the solvent driven off on the water bath in a current of air, taking care that the temperature of the evaporating liquid does not rise much above 20 C. The dichloramine-T is then left as long, colorless, flattened, foursided prisms. This toluene-p-sulphondichloramide may be represented by the formula T and dichloramine-T and chloramines of carboxy acids are 'excellent destructive agents for the conversion of such vesicants as mustard gas into non-vesicant compounds, except as regards the stability of the same on cloth, as they deteriorate when exposed to sunlight and moisture. In selecting a material more suitable for rendering clothing protective against mustard gas, therefore, it becomes essential to find a material having the same activity as the compounds mentioned, but possessive of the desired property of stability.

The unstability of chloramines of carboxy acids results from the migration of the active chlorine atoms to the ortho or para positions upon the aromatic ring, after which migration to these positions the chlorine atoms become entirely inactive. Manifestly, therefore, if these positions are already occupied by chlorine, the migration cannot occur and the compound will be stabilized.

Briefly, such'a compound may be prepared by the following steps: (1) chlorination of aniline in acetic acid solution; (2) purification of the resulting trichloraniline hydrochloride by washing with acetic acid and then with water; (3) condensation of trichloraniline and benzoyl chloride without a solvent; (4) chlorination of trichlorphenyl benzoylamine in carbon tetrachloride solution by (5) washing the product 2,926,107"- Patented Feb. 23, 115.60

benzoyl chloramine, represented by the following formula More specifically, the desired 2-4-6 trichlorphenyl benzoyl chloramine .is preferably prepared as follows. Aniline is dissolved in seven times its weight of glacial acetic acid and a rapid stream of chlorine gas passed thereinto, the mixture being continuously agitated. This chlorination should continue until the gain in weight is 2.29 parts per part of aniline used, which is. the theoretical .gain required for the formation of trichloraniline, assuming all the HCl to be retained. Using 400 grams of aniline and 2800 grams of acetic acid, this chlorination takes about 6.5 hours.

The precipitate is filtered off and washed, with a small amount of acetic acid until the filtrate is clear and is then washed with water. The trichloraniline hydrochloride obtained melts at 78-79 C. without crystallization.

use on clothing it will retain its activity The triohloraniline hydrochloride is then rubbed in with benzoyl chloride (about 10 percent more than theory) in which it is dissolved completely. This solution is then heated in a water or other bath and the 2-4-6 triohlorphenyl benzoylamine solidifies, the condensation mass being stirred at frequent intervals to prevent solidification to the hard cake. The 2-4-6 trichlorphenyl benzoylamine is then treated with an additional 10 percent of benzoyl chloride and heated for about two hours further on a water bath in an open receptacle. This latter treatment drives off all hydrogen chloride and leaves the free base without the occurrence of any hydrolysis.

The treatment of trichloraniline with benzoyl chloride to form trichlorphenyl benzoyl amine may be represented by the following 7 NH: 00 C] N- 0 c1 1 Cl[ 1 The 2-4-6 trichlorphenyl benzoylamine is next chlorinated by dissolving it in a glacial acetic acid or carbon tetrachloride solution by means of sodium hypochlorite to replace the remaining hydrogen on the nitrogen by chlorine. To each gram of the amine, about 12 cc. of acetic acid should be used, and the mixture heated by a water bath until solution is complete, generally at 60-70 C. The solution is then allowed to cool to about 50 C. and is treated cautiously with an aqueous solution of I have found 2-4-6-trichlorphenyl benzoyl chloramine to be a stabilized elfective destroyer of such vesicant gases as mustard, and of the same activity as the compounds which do not contain halogen atoms in the aromatic ring. I have proved it in practiceto be stable against sunlight, airandwater. I havefound it to be many times more stable on cloth than chloramine-T or dichloramine-T when exposed to sunlight, air and Water. In fora month or more whereas dichloramine-T is: completely decomposed in 10 days or less, under the same condition of use.

I have found that similarly 2-4-6 trichlorphenyl acetyl chloramine is an efiective destructive agent for vesicants such as mustard gas. This compound may be prepared by dissolving trichloraniline in carbon tetrachloride, treating with acetyl-chloride in slight excess (20%) and the materials refluxed for about one hour. The free amine, which is insoluble in carbon tetrachloride, begins to crystallize out within 10 minutes. After evaporating ofi the carbon tetrachloride, the solid is recrystallized from alcohol, and then has a melting point of about 203 C. This compound may then be chlorinated by means of sodium hypochlorite as described above in connection with the preparation of 2-4-6 trichlorphenyl benzoyl chloramine. chloramine is a white powder melting at 73 C. and analyzing 100 percent pure.

I have determined that these stabilized compounds, the

activity of which is effective in the same degree as.

chloramines of sulphonic acid, such as chloramine-T, and chloramines of carboxy acids, may be introduced into any fabric, and further that fabrics so treated will protect the rendering cloth protective against sodium hypochlorite containing about 5 grams available chlorine per 100 cc., the total amount used being 20 percent in excess of theory. For a solution of 500 grams of the amine in 6000 cc. of acetic acid, 1400 cc. of a 10 percent solution of sodium hypochlorite has been found to give good results, the treatment requiring about two hours. I

The 2-4-6 trichlorphenyl benzoyl chloramine obtained in fine granular crystals requiring no purification.

This chlorination may be represented by the following body wholly against vesicants, such as mustard, for a period of hours, under conditions more exacting than occur in actual practice.

In order to obtain the highest degree of mustard destructive efiiciency, I have found it advantageous to disperse and fix the chloramine on the cloth my means of a suitable carrier or vehicle, for example, highly chlorinated paraffin. By this means a greater surface of the chloramine is presented to the vesicant, and the cloth retains its good appearance. Furthermore, because the highly chlorinated parafiin is non-reactive with chlorine, it is therefore non-reactive with the chlorine of the chloramine.

I prefer to use 2-4-6 trichlorphenyl benzoyl-chloramine dispersed in chlorinated paraflin as an impregnant for vesicant gases such as mustard gas.

Any suitable method for impregnating cloth or other protective fabrics with any of the elfective compounds may be followed. I have found that the solution of any: of the compounds in a suitable carrier which may be diluted by a volatile solvent is efiective'for impregnating fabric, the fabric being immersed therein for a suitable period.

. The following specific example will serve to illustrate the method of impregnation, although it is not intended as a limitation of, the scope of the invention:

The cloth to be impregnated'is immersed in 'a solution consisting of carbon tetrachloride which contains 10 percent by weight of 2-4-6 trichlorphenyl benzoyl chloramine and 10 percent by weight offchlorinated paraflin. After complete saturation the cloth is removed from the solution and put through squeeze rolls to remove that amount of solution which is in excess of a weight equivalent to the weight of the cloth. The carbon tetrachloride is then The resulting 2-4-6 trichlorpheny1 acetyl tioned, my invention is applicable to both cotton and woolen fabrics or cloth made from any other material, such as linen or silk.

In addition to having properties suitable for vesicant substances, such as mustard gas vapors and similar substances, which may be non-vesicant, the compounds hereinbefore set forth are also effective as germicides and disinfectants. When used in this connection, the material may be employed alone or in combination with other substances. I

In the foregoing description and accompanying claims, the terms vesicants, vesicant gases or vapors are intended to include gases, vapors and liquids. The term mustard gas designates the vesicant compound bis(beta-chlorethyl) sulphide which may be in the gaseous, vapor, or liquid state.

While I have described the preferred embodiments of my invention, I wish it to be clearly understood that I do not confine myself to the precise steps or ingredients set forth herein by way of illustration, as it is apparent that many changes and variations may be made therein by those skilled in the art without departing from the spirit of the invention or exceeding the scope of the appended claims.

I claim:

protection against vesicant gases containing impregnated therein a member of the group consisting of 2-4-6 trichlorphenyl benzoyl chloramine and 2-4-6 trichlorphenyl acetyl chloramine dispersed in a vehicle non-reactive to chlorine.

3. A cloth for use in protection against vesicant gases containing impregnated therein a member of the group consisting of 2-4-6 trichlorphenyl benzoyl chloramine and 2-4-6 trichlorphenyl acetyl chloramine dispersed in chlorinated paraffin.

4. A cloth for use in protection against vesicant gases containing 2-4-6-trichlorphenyl benzoyl chloramine impregnated therein.

containing impregnated therein 2-4-6-trichlorphenyl acetyl chloramine dispersed in a vehicle non-reactive to chlorine.

8. A cloth for use in protection against vesicant gases containing impregnated therein 2-4-6-trichlorphenyl benzoyl chloramine dispersed in chlorinated paraflin.

9. A cloth for use in protection against vesicant gases containing impregnated therein 2-4-6-trichlorphenyl acetyl chloramine dispersed in chlorinated paratfin.

References Cited in the file of this patent UNITED STATES PATENTS 1,839,168 Stampe Dec. 29, 1931 FOREIGN PATENTS 514,094 Germany Dec. 13, 1930 731,395 France Sept. 2, 1932 735,765 France Nov. 15, 1932 OTHER REFERENCES Journal Chemical Society, Gurney and Jackson, 1, Paternoster Row, London, England (1900), vol. 77,

part 1, page 136.

Chattaway et al.: pages 1073 to 1078.

Chattaway: Jour. Chem. Soc. vol. 87, pages 145, 146 et seq.

New Standard Formulary, I-Iiss and Hibbcrt (1920), pages 186-192.

The Medical Aspects of Chemical Warfare," Vedder (1925), pages -156, 213, 214.

New and Non-Oificial Remedies (1930), page 194.

The Extra Pharmacopoeia, Martindale et 211., vol. I (1932), pages 46, 47, 48.

Her. deut. Chem, vol. 34 (1901),

(London), (1905), 

1. A CLOTH FOR USE IN PROTECTING AGAINST VESICANT GASES CONTAINING A MEMBER OF THE GROUP CONSISTING OF 2-4-6 TRICHLORPHENYL BENZOYL CHLORAMINE AND 2-4-6 TRICHLORPHENYL ACETYL CHLORAMINE IMPREGNATED THEREIN. 